Water-soluble unit dose articles made from a combination of different films

ABSTRACT

The present disclosure relates to pouches made from a combination of chemically different water-soluble films and optionally containing a composition (e.g. a household care composition or non-household care composition) that is at least partially enclosed by the water-soluble films in at least one compartment.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 15/620,316,filed Jun. 12, 2017, which claims the benefit under 35 U.S.C. § 119(e)of U.S. Provisional Patent Application No. 62/349,655 filed Jun. 13,2016. The entire disclosures of the foregoing applications areincorporated herein by reference.

Names of Parties to a Joint Research Agreement

The parties are MonoSol, LLC and Procter & Gamble Company.

FIELD

The present disclosure relates to water-soluble unit dose articles madefrom a combination of chemically different water-soluble films andoptionally containing a composition, e.g. a household care compositionor non-household care composition, that is at least partially enclosedby the water-soluble films in at least one compartment.

BACKGROUND

Water-soluble polymeric films are commonly used as packaging materialsto simplify dispersing, pouring, dissolving and dosing of a material tobe delivered. For example, water-soluble unit dose articles made fromwater-soluble film are commonly used to package household carecompositions, e.g., a pouch containing a laundry or dish detergent, andnon-household care compositions, e.g. a pouch containing a watertreatment active agent. A user (e.g., a consumer) can directly add thewater-soluble unit dose article to a mixing vessel, such as a bucket,sink or washing machine, or to the water tank of a toilet, or to aswimming pool. Advantageously, this provides for accurate dosing whileeliminating the need for the consumer to measure the composition. Thewater-soluble unit dose article may also reduce mess that would beassociated with dispensing a similar composition from a vessel, such aspouring a liquid laundry detergent from a bottle or dispensing watertreatment granules or pellets from a bucket. The water-soluble unit dosearticle also insulates the composition therein from contact with theuser's hands. In sum, water-soluble unit dose articles containingpre-measured agents provide for convenience of consumer use in a varietyof applications.

Some water-soluble polymeric films that are used to make water-solubleunit dose articles will incompletely dissolve during a wash cycle,leaving film residue on items within the wash. Such problems mayparticularly arise when the water-soluble unit dose article is usedunder stressed wash conditions, such as when the pouch is used in coldwater (e.g., water as low as 5° C. and/or up to 10° C. or 15° C.), withshort water contact times, e.g. in a short wash cycle, and/or with lowconcentrations of water available for film dissolution, e.g. in alow-water wash cycle (e.g., wash liquors from about 3 L to about 20 Lfor pouches sized to contain 5 mL to 300 mL contents, for example).Notably, environmental concerns and energy cost are driving consumerdesire for utilizing colder wash water and shorter wash cycles inlaundry applications.

Some water-soluble polymeric films that are used to make water-solubleunit dose articles will completely dissolve during a wash cycle but areso substantive to water that the films will become sticky when exposedto high humidity conditions, causing water-soluble unit dose articlesmade thereof to stick together when exposed to such high humidityconditions during manufacturing or upon storage in the container duringtransport, at a warehouse or in consumers' home.

Additionally, it is desirable for the water-soluble unit dose article tohave an adequate strength, both soon after making and upon storage, towithstand forces that may be applied during packing, transport, storage,and usage. Adequate strength may be particularly preferred with thepouches encapsulate liquid compositions, such as laundry detergent ordye concentrates, to avoid unintentional bursting and/or leakage.

There remains a need for water-soluble films and water-soluble unit dosearticles, such as pouches, having the desired characteristics of goodwater solubility, reduced sticking, suitable pouch strength, chemicalresistance, chemical and physical compatibility with laundry actives orother compositions in contact with the film or water-soluble unit dosearticle formed therefrom, and/or desirable mechanical properties, suchas deformability upon thermoforming and/or adequate sealing. It has beenfound that water-soluble unit dose articles according to the presentdisclosure exhibits optimal water solubility and reduced stickiness.

SUMMARY OF THE INVENTION

The present disclosure relates to a water-soluble unit dose articlecomprising at least one sealed compartment optionally comprising atleast one composition (e.g. a household care composition or anon-household care composition), the water-soluble unit dose articlecomprising a first water soluble film and a second water soluble film,wherein the first film is sealed to the second film to form the at leastone sealed compartment, wherein the first water-soluble film ischemically different from the second water soluble film with respect tothe anionic content of the films.

The present disclosure also relates to methods of making and using suchpouches.

BRIEF DESCRIPTION OF THE DRAWINGS

The figures herein are illustrative in nature and are not intended to belimiting.

FIG. 1 shows a schematic illustration of the basic configuration of theunit dose article strength test and seal failure test.

FIG. 2 shows a side cross-sectional view of a pouch.

FIG. 3 shows a multi-compartment pouch.

FIG. 4 shows a graph of the increased pouch dissolution of the unit dosearticles as described herein.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the articles “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described. As usedherein, the terms “include,” “includes,” and “including” are meant to benon-limiting. The compositions of the present disclosure can comprise,consist essentially of, or consist of, the components of the presentdisclosure.

The terms “substantially free of” or “substantially free from” may beused herein. This means that the indicated material is at the veryminimum not deliberately added to the composition to form part of it,or, preferably, is not present at analytically detectable levels. It ismeant to include compositions whereby the indicated material is presentonly as an impurity in one of the other materials deliberately included.The indicated material may be present, if at all, at a level of lessthan 1%, or less than 0.1%, or less than 0.01%, or even 0%, by weight ofthe composition.

The water-soluble unit dose articles of the present disclosure includeembodiments of packages themselves, and packages which may contain acomposition, for example a household care composition or a non-householdcare composition. The composition can be selected from a liquid, solidor combination thereof. As used herein, “liquid” includes free-flowingliquids, as well as pastes, gels, foams and mousses. Non-limitingexamples of liquids include light duty and heavy duty liquid detergentcompositions, fabric enhancers, detergent gels commonly used forlaundry, bleach and laundry additives. Gases, e.g., suspended bubbles,or solids, e.g. particles, may be included within the liquids. A “solid”as used herein includes, but is not limited to, powders, agglomerates,and mixtures thereof. Non-limiting examples of solids include: granules,micro-capsules, beads, noodles, and pearlised balls. Solid compositionsmay provide a technical benefit including, but not limited to,through-the-wash benefits, pre-treatment benefits, and/or aestheticeffects.

As used herein, the term “homopolymer” generally includes polymershaving a single type of monomeric repeating unit (e.g., a polymericchain consisting of or consisting essentially of a single monomericrepeating unit). For the particular case of polyvinyl alcohol (PVOH),the term “homopolymer” (or “PVOH homopolymer” or “PVOH polymer”) furtherincludes copolymers having a distribution of vinyl alcohol monomer unitsand vinyl acetate monomer units, depending on the degree of hydrolysis(e.g., a polymeric chain consisting of or consisting essentially ofvinyl alcohol and vinyl acetate monomer units). In the limiting case of100% hydrolysis, a PVOH homopolymer can include a true homopolymerhaving only vinyl alcohol units.

As used herein, the term “copolymer” generally includes polymers havingtwo or more types of monomeric repeating units (e.g., a polymeric chainconsisting of or consisting essentially of two or more differentmonomeric repeating units, whether as random copolymers, blockcopolymers, etc.). For the particular case of PVOH, the term “copolymer”(or “PVOH copolymer”) further includes copolymers having a distributionof vinyl alcohol monomer units and vinyl acetate monomer units,depending on the degree of hydrolysis, as well as at least one othertype of monomeric repeating unit (e.g., a ter- (or higher) polymericchain consisting of or consisting essentially of vinyl alcohol monomerunits, vinyl acetate monomer units, and one or more other monomer units,for example anionic monomer units). In the limiting case of 100%hydrolysis, a PVOH copolymer can include a copolymer having vinylalcohol units and one or more other monomer units, but no vinyl acetateunits.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All temperatures herein are in degrees Celsius (° C.) unless otherwiseindicated. Unless otherwise specified, all measurements herein areconducted at 20° C., under atmospheric pressure, and at 50% relativehumidity.

In the present disclosure, all percentages are by weight of the totalcomposition, unless specifically stated otherwise. All ratios are weightratios, unless specifically stated otherwise.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All ranges set forth herein include all possible subsets of ranges andany combinations of such subset ranges. By default, ranges are inclusiveof the stated endpoints, unless stated otherwise. Where a range ofvalues is provided, it is understood that each intervening value betweenthe upper and lower limit of that range and any other stated orintervening value in that stated range, is encompassed within thedisclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges, and are alsoencompassed within the disclosure, subject to any specifically excludedlimit in the stated range. Where the stated range includes one or bothof the limits, ranges excluding either or both of those included limitsare also contemplated to be part of the disclosure.

It is expressly contemplated that for any number value described herein,e.g. as a parameter of the subject matter described or part of a rangeassociated with the subject matter described, an alternative which formspart of the description is a functionally equivalent range surroundingthe specific numerical value (e.g. for a dimension disclosed as “40 mm”an alternative embodiment contemplated is “about 40 mm”).

Water-Soluble Unit Dose Article

The water-soluble unit dose article described herein comprises a firstwater-soluble film and a second water-soluble film shaped such that theunit-dose article comprises at least one internal compartment surroundedby the water-soluble films. The water-soluble films are sealed to oneanother such to define the internal compartment, and in a completed,filled article the films are sealed to one another such that that thedetergent or other composition does not leak out of the compartmentduring storage. However, upon addition of the water-soluble unit dosearticle to water (or vice-vera), the water-soluble film dissolves andreleases the contents of the internal compartment, e.g. into the wateror wash liquor. The water-soluble unit dose article may be a pouch.

The area in which the two films meet and are sealed together is referredto as the seal area. Often, the seal area comprises a ‘skirt’ or‘flange’ which comprises area of the first water-soluble film sealed toan area of the second water-soluble film and which generally protrudesout from the main body of the unit dose article. A preferred method ofmaking a unit dose article is described in more detail below.

The compartment should be understood as meaning a closed internal spacewithin the unit dose article, which can hold a detergent or othercomposition. During manufacture, the first water-soluble film accordingto the present invention may be shaped to comprise an open compartmentinto which the detergent or other composition is added. The secondwater-soluble film according to the present invention is then laid overthe first film in such an orientation as to close the opening of thecompartment. The first and second films are then sealed together along aseal region.

The unit dose article may comprise more than one compartment, even atleast two compartments, or even at least three compartments. Thecompartments may be arranged in superposed orientation, i.e. onepositioned on top of the other. In such an orientation the unit dosearticle will comprise three films, top, middle and bottom. Preferably,the middle film will correspond to the second water-soluble filmaccording to the present invention and top and bottom films willcorrespond to the first water-soluble film according to the presentinvention. Alternatively, the compartments may be positioned in aside-by-side orientation, i.e. one orientated next to the other. Thecompartments may even be orientated in a ‘tyre and rim’ arrangement,i.e. a first compartment is positioned next to a second compartment, butthe first compartment at least partially surrounds the secondcompartment, but does not completely enclose the second compartment.Alternatively one compartment may be completely enclosed within anothercompartment. In such a multicompartment orientation, the firstwater-soluble film according to the present invention may be shaped tocomprise an open compartment into which the detergent or othercomposition is added. The second water-soluble film according to thepresent invention is then laid over the first film in such anorientation as to close the opening of the compartment.

Wherein the unit dose article comprises at least two compartments, oneof the compartments may be smaller than the other compartment. Whereinthe unit dose article comprises at least three compartments, two of thecompartments may be smaller than the third compartment, and preferablythe smaller compartments are superposed on the larger compartment. Thesuperposed compartments preferably are orientated side-by-side.

In a multi-compartment orientation, a composition (e.g. a non-householdcare composition) may be comprised in at least one of the compartments.It may, for example, be comprised in just one compartment, or may becomprised in two compartments, or even in three compartments. Forexample, in a multi-compartment orientation, the detergent compositionaccording to the present invention may be comprised in at least one ofthe compartments. Alternatively the detergent may, for example, becomprised in just one compartment, or may be comprised in twocompartments, or even in three compartments

Each compartment may comprise the same or different compositions. Thedifferent compositions could all be in the same form, or they may be indifferent forms.

The water-soluble unit dose article may comprise at least two internalcompartments, wherein a liquid composition is comprised in at least oneof the compartments, preferably wherein the unit dose article comprisesat least three compartments, wherein the liquid composition is comprisedin at least one of the compartments. For example, a water-soluble unitdose detergent article may comprise at least two internal compartments,wherein the liquid laundry detergent composition is comprised in atleast one of the compartments, preferably wherein the unit dose articlecomprises at least three compartments, wherein the detergent compositionis comprised in at least one of the compartments.

First and Second Water-Soluble Films

The water-soluble unit dose article comprises a first water-soluble filmand a second water-soluble film and the first water-soluble film and thesecond water-soluble film are chemically different to one another.

For the avoidance of doubt, in the context of the present invention‘chemically different’ herein means where the ‘virgin films’, i.e. filmsreceived from the supplier/manufacture and prior to unwinding on a unitdose article making unit, having at least one substance present in atleast one of the film compositions that differentiates the first fromthe second film composition and impacts at least one of the physicalproperties of the film, such as water capacity, elongation modulus, andtensile strength at break, per the test method(s) described herein,rendering this at least one physical film property different between thefirst and second films. Varying chemical compositions of films due tonatural making processes i.e. batch to batch variations are as such notconsidered chemically different films within the scope of thisinvention.

Non limiting examples of chemically differentiating substances includeuse of different polymer target resins and or content, differentplasticizer composition and or content or different surfactant and orcontent. Water soluble unit dose articles comprising films solelydiffering in physical properties but having the same substance content,such as films solely differing in film thickness, are considered outsidethe scope of this invention. Unit dose articles made from films beingsolely differentiated through the presence versus the absence of acoating layer are also considered outside the scope of the invention.

Preferably, the first water-soluble film is thermoformed duringmanufacture of the unit dose article. By ‘thermoforming’ we herein meanthat the film is heated prior to deformation, for example, by passingthe film under an infrared lamp, the deformation step preferably beingenabled by laying the water soluble film over a cavity and applyingvacuum or an under pressure inside the cavity under the film. The secondwater-soluble film may be thermoformed during manufacture of the unitdose article. Alternatively the second water-soluble film may not bethermoformed during manufacture of the unit dose article. Preferably,the first water-soluble film is thermoformed during manufacture of theunit dose article and the second water-soluble film is not thermoformedduring manufacture of the unit dose article.

The first water-soluble film and the second water-soluble film each mayindependently have a thickness before incorporation into the unit dosearticle of between 40 microns and 100 microns, preferably between 60microns and 90 microns, more preferably between 70 microns and 80microns.

Preferably the difference in thickness before incorporation into theunit dose article between the first water-soluble film and the secondwater-soluble film is less than 50%, preferably less than 30%, morepreferably less than 20%, even more preferably less than 10%, or thethicknesses may be equal.

The first water-soluble film and the second water-soluble film accordingto the invention are preferably single layer films, more preferablymanufactured via solution casting.

The water-soluble film can further have a residual moisture content ofat least 4 wt. %, for example in a range of about 4 to about 10 wt. %,as measured by Karl Fischer titration.

The first water-soluble film and/or the second water-soluble filmdescribed herein may contain polymers, e.g., PVOH polymers, whichcomprise anionic monomer units. The amount of anionic monomer unitspresent in the first water-soluble film and/or the second water-solublefilm may be expressed in terms of anionic content. The firstwater-soluble film may have a first anionic content and the secondwater-soluble film may have a second anionic content. The first anioniccontent may be different from the second anionic content. By “anioniccontent” it is meant the anionic monomer units present in the PVOHpolymer of the film, for example as molar content (mol. %) of theanionic monomer units compared to the total amount of PVOH polymer inthe film (e.g., total of PVOH polymer, including homopolymer(s) andcopolymer(s)). The amount of anionic monomer units may be characterizedin terms of the molar content (expressed, e.g., as mol. %) of theanionic monomer units in a polymer, e.g., a PVOH copolymer. The one ormore anionic monomer units may be present in the PVOH copolymer in anamount in a range of from about 1 mol. % to about 10 mol. %, or fromabout 2 mol. % to about 8 mol. %, or from about 2 mol % to about 6 mol%, or from about 3 mol % to about 6 mol %, or from about 1 mol % toabout 4 mol %, or from about 3 mol % to about 5 mol %, or from about 3.5mol. % to about 4.5 mol %, or from about 4 mol. % to about 4.5 mol. %,individually or collectively. The anionic monomer unit(s) may be presentin the PVOH copolymer in an amount of at least about 3.0 mol %, at leastabout 3.5 mol %, at least about 4.0 mol. %, and/or up to about 6.0 mol%, up to about 5.5 mol %, up to about 5.0 mol %, or up to about 4.5 mol.%.

The water-soluble unit dose article disclosed herein may comprise afirst water soluble film comprising a first anionic content and a secondwater soluble film comprising a second anionic content, where the firstanionic content is greater than the second anionic content. Thedifference between the first anionic content and the second anioniccontent is about 0.05 mol % to about 4 mol %, or about 0.1 mol % toabout 2 mol %, or about 0.2 mol % to about 1 mol %. The first anioniccontent may comprise a first type of anionic monomer unit and the secondanionic content may comprise a second type of anionic monomer unit.

The first water-soluble film and the second water-soluble film mayindependently comprise from about 0 mol. % to about 10 mol. % of anionicmonomer unit(s) compared to the total amount of PVOH polymer in thefilm. The first water-soluble film and the second water-soluble film mayindependently comprise at least about 0.25 mol. %, at least about 0.5mol. %, at least about 0.75 mol. %, at least about 1.0 mol. %, at leastabout 1.25 mol. %, or at least about 1.5 mol. % and/or up to about 7.5mol. %, up to about 5.0 mol. %, up to about 4.0 mol. %, up to about 3.0mol. %, up to about 2.0 mol. %, or up to about 1.5 mol. % of anionicmonomer unit(s) compared to the total amount of PVOH polymer in thefilm. For example, for a film comprising a 50 wt %/50 wt % blend of twoPVOH polymers, where the first PVOH polymer is a copolymer that includes4 mol. % anionic monomer units and the second PVOH polymer is ahomopolymer, the anionic content is about 2.0 mol. % of total PVOHpolymer. Or, for example, for a film comprising a 50 wt %/50 wt % blendof two PVOH polymers, where the first PVOH polymer is a copolymer thatincludes 4 mol. % anionic monomer units and the second PVOH polymer is acopolymer that includes 2 mol. % anionic monomer units, the anioniccontent is about 3.0 mol. % of total PVOH polymer. Or, for example, fora film comprising a 100 wt % of a PVOH copolymer that includes 4 mol. %anionic monomer units, the anionic content is about 4.0 mol. % of totalPVOH polymer.

Thus, for a film comprising a blend of two PVOH polymers, where thefirst PVOH polymer is a copolymer that includes anionic monomer unitsand the second PVOH polymer is a homopolymer, the anionic content of thefilm may be increased by increasing the mol. % anionic monomer units inthe copolymer or increasing the wt % of copolymer in thecopolymer/homopolymer blend.

The PVOH copolymer can include two or more types of anionic monomerunits. Preferably, the PVOH copolymer includes a single type of anionicmonomer unit.

The anionic monomer unit may be selected from the group consisting ofanionic monomers derived from of vinyl acetic acid, alkyl acrylates,maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate,dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate,dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaricanhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate,itaconic anhydride, citraconic acid, monoalkyl citraconate, dialkylcitraconate, citraconic anhydride, mesaconic acid, monoalkyl mesaconate,dialkyl mesaconate, mesaconic anhydride, glutaconic acid, monoalkylglutaconate, dialkyl glutaconate, glutaconic anhydride, vinyl sulfonicacid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropane sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts thereof, esters thereof, and combinations thereof;

Preferably, the anionic monomer unit is selected from the groupconsisting of anionic monomers derived from maleic acid, monoalkylmaleate, dialkyl maleate, maleic anhydride, alkali metal salts thereof,esters thereof, and combinations thereof;

More preferably the anionic monomer unit is selected from the groupconsisting of anionic monomers derived from maleic acid, monomethylmaleate, dimethyl maleate, maleic anyhydride, alkali metal saltsthereof, esters thereof, and combinations thereof.

The first water soluble film may comprise a first water soluble resinand the second water soluble film may comprise a second water solubleresin. The first water soluble resin may be chemically different fromthe second water soluble resin. Preferably, the first water solubleresin comprises at least one polyvinyl alcohol homopolymer or at leastone polyvinyl alcohol copolymer or a blend thereof and the second watersoluble resin comprises at least one polyvinyl alcohol homopolymer or atleast one polyvinyl alcohol copolymer or a blend thereof, provided thatat least one of the first water-soluble resin or the secondwater-soluble resin comprises at least one polyvinyl alcohol copolymercomprising an anionic monomer unit.

The first water soluble resin may comprise a blend of a polyvinylalcohol homopolymer and a polyvinyl alcohol copolymer comprising ananionic monomer unit, optionally wherein the blend comprises from 0% to70% by weight of the first water soluble resin of the polyvinyl alcoholcopolymer comprising an anionic monomer unit and from 30% to about 100%by weight of the first water soluble resin of the polyvinyl alcoholhomopolymer. The blend can comprise from 10% to 70%, or from 15% toabout 65%, or from 20% to 50%, or from 30% to 40% of the polyvinylalcohol copolymer comprising an anionic monomer unit, based on the totalweight of the first water soluble resin. In another type of embodiment,the blend comprises 65 wt. % or greater of an anionic polyvinyl alcoholcopolymer, or greater than 65 wt. % of an anionic polyvinyl alcoholcopolymer.

The second water soluble resin may comprise a blend of a polyvinylalcohol homopolymer and a polyvinyl alcohol copolymer comprising ananionic monomer unit, optionally wherein the blend comprises from 0% to70% of the polyvinyl alcohol copolymer comprising an anionic monomerunit and from 30% to 100% of the polyvinyl alcohol homopolymer, based onthe total weight of the second water soluble resin in the film. Theblend can comprise from 10% to 70%, or from 15% to 65%, or from 20% to50%, or from 30% to 40% of the polyvinyl alcohol copolymer comprising ananionic monomer unit, based on the total weight of the second watersoluble resin in the film. In another type of embodiment, the blendcomprises 65 wt. % or greater of an anionic polyvinyl alcohol copolymer,or greater than 65 wt. % of an anionic polyvinyl alcohol copolymer.

The first water soluble resin and the second water soluble resin mayalso comprise different polyvinyl alcohol copolymers comprising anionicmonomer units.

Preferably, the at least one polyvinyl alcohol homopolymer or the atleast one polyvinyl alcohol copolymer or the blend thereof of the firstwater-soluble film and the at least one polyvinyl alcohol homopolymer orthe at least one polyvinylalcohol copolymer or the blend thereof of thesecond water-soluble film independently have a 4% solution viscosity indemineralized water at 25° C. in a range of 4 cP to 40 cP, preferably of10 cP to 30 cP, more preferably of 11 cP to 26 cP. More preferably, thefirst water soluble resin comprises at least one polyvinyl alcoholhomopolymer or at least one polyvinylalcohol copolymer or a blendthereof having a 4% solution viscosity in demineralized water at 25° C.in a range of about 8 cP to about 40 cP, or about 12 cP to about 30 cP,or about 14 cP to about 26 cP and the second water soluble resincomprises at least one polyvinyl alcohol homopolymer or at least onepolyvinylalcohol copolymer or a blend thereof having a 4% solutionviscosity in demineralized water at 25° C. in a range of about 4 cP toabout 35 cP, or about 10 cP to about 20 cP, or about 10 cP to about 15cP, or about 11 cP to about 14 cP.

Preferably, the 4% solution viscosity in demineralized water at 25° C.of the at least one polyvinyl alcohol homopolymer or the at least onepolyvinylalcohol copolymer or the blend thereof of the first watersoluble resin is greater than the 4% solution viscosity in demineralizedwater at 25° C. of the at least one polyvinyl alcohol homopolymer or theat least one polyvinylalcohol copolymer or the blend thereof of thesecond water soluble resin. More preferably, the difference between the4% solution viscosity in demineralized water at 25° C. of the at leastone polyvinyl alcohol homopolymer or the at least one polyvinylalcoholcopolymer or the blend thereof of the first water soluble resin and the4% solution viscosity in demineralized water at 25° C. of the at leastone polyvinyl alcohol homopolymer or the at least one polyvinylalcoholcopolymer or the blend thereof of the second water soluble resin isabout 2 cP about 20 cP, or about 3 cP to about 15 cP, or about 4 cP toabout 12 cP.

By ‘difference’ we herein mean the difference in the value of the 4%solution viscosity in demineralized water at 25° C. of the at least onepolyvinyl alcohol homopolymer or the at least one polyvinylalcoholcopolymer or the blend thereof of the first water soluble resin and thevalue of the 4% solution viscosity in demineralized water at 25° C. ofthe at least one polyvinyl alcohol homopolymer or the at least onepolyvinylalcohol copolymer or the blend thereof of the second watersoluble resin.

When the first water-soluble resin and the second water-soluble resineach comprises a blend of a polyvinyl alcohol homopolymer and apolyvinyl alcohol copolymer comprising an anionic monomer unit, thepolyvinyl alcohol copolymer comprising an anionic monomer unit of thefirst water-soluble resin may have a first viscosity (μ_(c1)); thepolyvinyl alcohol copolymer comprising an anionic monomer unit of thesecond water-soluble resin may have a second viscosity (μ_(c2)); thepolyvinyl alcohol homopolymer of the first water-soluble resin may havea first viscosity (μ_(h1)); the polyvinyl alcohol homopolymer of thesecond water-soluble resin may have a second viscosity (μ_(h2)); thefirst water-soluble resin may have a blend viscosity (μ_(blend1)); andthe second water-soluble resin may have a blend viscosity (μ_(blend2)).Blend viscosities are weight averaged and may be calculated as follows:blend viscosity=e{circumflex over ( )}(w₁(ln μ_(c1))+w₂(ln μ_(h1))),where e is Euler's number and w is weight % based on the total weight ofthe respective water soluble resin. And, the viscosity difference may becalculated in a number of ways:|μ_(c1)−μ_(c2)|>0, when μ_(h2)=μ_(h1);  (i)|μ_(h1)−μ_(h2)|>0, when μ_(c2)=μ_(c1);  (ii)|μ_(blend1)−μ_(blend2)|>0.  (iii)

Preferably, the first polyvinyl alcohol homopolymer and second polyvinylalcohol homopolymer and the first polyvinyl alcohol copolymer and secondpolyvinyl alcohol copolymer independently have a degree of hydrolysis offrom 80% to 99% preferably from 85% to 95% more preferably from 87% and93%.

Preferably, the first water-soluble film and the second water-solublefilm independently have a water soluble resin content of between 30% and90%, more preferably between 40% and 80%, even more preferably between50% and 75%, most preferably between 60% and 70% by weight of the film.

Other water soluble polymers for use in addition to the first polyvinylalcohol homopolymers and second polyvinyl alcohol homopolymer and firstpolyvinyl alcohol copolymer and second polyvinyl alcohol copolymer caninclude, but are not limited to a vinyl alcohol-vinyl acetate copolymer,sometimes referred to as a PVOH homopolymer, polyacrylates,water-soluble acrylate copolymers, polyvinyl pyrrolidone,polyethyleneimine, pullulan, water-soluble natural polymers including,but not limited to, guar gum, gum Acacia, xanthan gum, carrageenan, andstarch, water-soluble polymer derivatives including, but not limited to,modified starches, ethoxylated starch, hydroxyethylated starch andhydroxypropylated starch, copolymers of the forgoing and combinations ofany of the foregoing. Yet other water-soluble polymers can includepolyalkylene oxides, polyacrylamides, polyacrylic acids and saltsthereof, celluloses, cellulose ethers, cellulose esters, celluloseamides, polyvinyl acetates, polycarboxylic acids and salts thereof,polyaminoacids, polyamides, gelatines, methylcelluloses,carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses,hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,polymethacrylates, and combinations of any of the foregoing. Suchwater-soluble polymers, whether PVOH or otherwise are commerciallyavailable from a variety of sources.

The first water-soluble film has a first water capacity, and the secondwater-soluble film has a second water capacity wherein the first watercapacity is less than the second water capacity.

The difference between the water capacity of the first water solublefilm and the second water-soluble film is between 0.01% and 1%,preferably from 0.03% to 0.5%, most preferably from 0.05% to 0.3%. Thefirst water-soluble film and the second water-soluble film are describedin more detail below. By ‘difference’ we herein mean the difference inthe value of the first water capacity and the value of the second watercapacity. By ‘water capacity’ we herein mean the capacity of the film toabsorb water over a fixed period of time at a particular relativehumidity and temperature, measured as a mass increase of the film beingtested. The method for measuring water capacity is described in moredetail below.

Preferably, the first water-soluble film has a water capacity from 1% to10%, more preferably from 2% to 8%, most preferably from 3% to 6%.

Preferably, the second water-soluble film has a water capacity from 1.5%to 12%, more preferably from 2.5% to 10%, most preferably from 3.5% to8%.

The first water-soluble film may have a first tensile strain at break ofbetween 300% and 1600%, preferably between 400% and 1200%, morepreferably between 600% and 1200%. The method to determine tensilestrain at break is described in more detail below.

The second water-soluble film may have a second tensile strain at breakof between 300% and 1200%, preferably between 500% and 1000%, morepreferably between 500% and 1000%. By tensile strain at break we hereinmean the ability of the film, pre-equilibrated with the compositionwhich it will contain, e.g. a detergent composition contacting the filmin a unit dose article comprising said film and detergent or othercomposition, to elongate prior to breaking when a stress is applied. Themethod to determine tensile strain at break is described in more detailbelow.

The difference between the first tensile strain at break and the secondtensile strain at break may be from 10% to 1000%, preferably from 100%to 750%, more preferably from 200% to 500%. By ‘difference in tensilestrain at break’ we herein mean the difference in the value of the firsttensile strain at break and the value of the second tensile strain atbreak.

Preferably, the first water soluble film has a first elongation modulus,the second water soluble film has a second elongation modulus, the firstelongation modulus is greater than the second elongation modulus, andthe difference between the first elongation modulus and the secondelongation modulus is from a 0.5 MPa to 10 MPa, preferably from 1 MPa to8 MPa, more preferably from 2 MPa to 7 MPa.

By ‘difference’ we herein mean the difference in the value of the firstelongation modulus and the value of the second elongation modulus. By‘elongation modulus’ we herein mean the ability of the film to beelongated when a stress is applied. The method for measuring elongationmodulus is described in more detail below.

Preferably, the first elongation modulus is from 1 MPa to 20 MPa, morepreferably from 3 MPa to 20 MPa.

Preferably, the second elongation modulus is from 1 MPa to 15 MPa, morepreferably from 3 MPa to 15 MPa.

Preferably, the water-soluble unit dose article exhibits a dissolutionprofile, according to the unit dose article dose article machine washdissolution test method described below of less than 6.2 preferably lessthan 6 more preferably less than 5.8.

The first and or second film may independently be opaque, transparent ortranslucent. The first and or second film may independently comprise aprinted area. The printed area may cover between 10 and 80% of thesurface of the film; or between 10 and 80% of the surface of the filmthat is in contact with the internal space of the compartment; orbetween 10 and 80% of the surface of the film and between 10 and 80% ofthe surface of the compartment.

The area of print may cover an uninterrupted portion of the film or itmay cover parts thereof, i.e. comprise smaller areas of print, the sumof which represents between 10 and 80% of the surface of the film or thesurface of the film in contact with the internal space of thecompartment or both.

The area of print may comprise inks, pigments, dyes, blueing agents ormixtures thereof. The area of print may be opaque, translucent ortransparent.

The area of print may comprise a single colour or maybe comprisemultiple colours, even three colours. The area of print may comprisewhite, black, blue, red colours, or a mixture thereof. The print may bepresent as a layer on the surface of the film or may at least partiallypenetrate into the film. The film will comprise a first side and asecond side. The area of print may be present on either side of thefilm, or be present on both sides of the film. Alternatively, the areaof print may be at least partially comprised within the film itself.

The area of print may be achieved using standard techniques, such asflexographic printing or inkjet printing. Preferably, the area of printis achieved via flexographic printing, in which a film is printed, thenmoulded into the shape of an open compartment. This compartment is thenfilled with a detergent or other composition and a second film placedover the compartment and sealed to the first film. The area of print maybe on either or both sides of the film.

Alternatively, an ink or pigment may be added during the manufacture ofthe film such that all or at least part of the film is coloured.

The first and or second film may independently comprise an aversiveagent, for example a bittering agent. Suitable bittering agents include,but are not limited to, naringin, sucrose octaacetate, quininehydrochloride, denatonium benzoate, or mixtures thereof. Any suitablelevel of aversive agent may be used in the film. Suitable levelsinclude, but are not limited to, 1 to 5000 ppm, or even 100 to 2500 ppm,or even 250 to 2000 ppm.

The first and/or second film may also comprise other secondaryingredient typically known by a skilled person in the art such as, butnot limited to, plasticizers, plasticizer compatibilizers, surfactants,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles such as layered silicate-type nanoclays (e.g., sodiummontmorillonite), bleaching agents (e.g., sodium metabisulfite, sodiumbisulfite or others), aversive agents such as bitterants (e.g.,denatonium salts such as denatonium benzoate, denatonium saccharide, anddenatonium chloride; sucrose octaacetate; quinine; flavonoids such asquercetin and naringen; and quassinoids such as quassin and brucine) andpungents (e.g., capsaicin, piperine, allyl isothiocyanate, andresinferatoxin), and other functional ingredients, in amounts suitablefor their intended purposes. Embodiments including plasticizers arepreferred. The amount of such agents can be up to about 50 wt. %, 20 wt%, 15 wt %, 10 wt %, 5 wt. %, 4 wt % and/or at least 0.01 wt. %, 0.1 wt%, 1 wt %, or 5 wt %, individually or collectively.

The plasticizer can include, but is not limited to, glycerin,diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethyleneglycol, dipropylene glycol, tetraethylene glycol, propylene glycol,polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane,polyether polyols, sorbitol, 2-methyl-1,3-propanediol (MPDiol®),ethanolamines, and a mixture thereof. A preferred plasticizer isglycerin, sorbitol, triethyleneglycol, propylene glycol, dipropyleneglycol, 2-methyl-1,3-propanediol, trimethylolpropane, or a combinationthereof. The total amount of the plasticizer can be in a range of about10 wt. % to about 45 wt. %, or about 15 wt. % to about 35 wt. %, orabout 20 wt. % to about 30 wt. %, or about 20 wt. % to about 45 wt. %,for example about 25 wt. %, based on total film weight. In embodiments,the amount of plasticizer in the water-soluble film is expressed inparts per 100 parts total water soluble polymer (PHR) in thewater-soluble film and is present at least 30 PHR, or at least 35 PHR,for example. The total amount of plasticizer can be up to 40 PHR or 45PHR or 50 PHR, for example. The total amount of plasticizer can be in arange of 30-50 PHR, about 32.5 PHR to about 42.5 PHR, or 35-45 PHR, or35-40 PHR, or greater than 30 PHR and less than 45 PHR, or 40 PHR to 50PHR, for example. The total amount of plasticizer can be 34 or 37.5 PHR.

Surfactants for use in water-soluble films are well known in the art.Optionally, surfactants are included to aid in the dispersion of theresin solution upon casting. Suitable surfactants can include thenonionic, cationic, anionic and zwitterionic classes. Suitablesurfactants include, but are not limited to, polyoxyethylenatedpolyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates,tertiary acetylenic glycols and alkanolamides (nonionics),polyoxyethylenated amines, quaternary ammonium salts and quaternizedpolyoxyethylenated amines (cationics), and amine oxides, N-alkylbetainesand sulfobetaines (zwitterionics). Other suitable surfactants includedioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerinand propylene glycol, lactylic esters of fatty acids, sodium alkylsulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate80, lecithin, acetylated fatty acid esters of glycerin and propyleneglycol, and acetylated esters of fatty acids, and combinations thereof.In embodiments, the surfactant is selected from the group consisting ofpolyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides,polyoxyethylenated amines, quaternary ammonium salts and quaternizedpolyoxyethylenated amines, and amine oxides, N-alkylbetaines,sulfobetaines, and combinations thereof.

In various embodiments, the amount of surfactant in the water-solublefilm is in a range of about 0.1 wt % to about 8.0 wt %, or about 1.0 wt% to about 7.0 wt %, or about 3 wt % to about 7 wt %, or about 5 wt % toabout 7 wt %. In embodiments, the amount of surfactant in thewater-soluble film is expressed in parts per 100 parts total watersoluble polymer (phr) in the water-soluble film and is present in arange of about 0.5 phr to about 12 phr, about 1.0 phr to about 11.0 phr,about 3.0 phr to about 10.5 phr, or about 1.0 phr to about 2.0 phr.

Suitable lubricants/release agents can include, but are not limited to,fatty acids and their salts, fatty alcohols, fatty esters, fatty amines,fatty amine acetates and fatty amides. Preferred lubricants/releaseagents are fatty acids, fatty acid salts, and fatty amine acetates. Inone type of embodiment, the amount of lubricant/release agent in thewater-soluble film is in a range of about 0.02 wt % to about 1.5 wt %,optionally about 0.1 wt % to about 1 wt %.

Suitable fillers/extenders/antiblocking agents/detackifying agentsinclude, but are not limited to, starches, modified starches,crosslinked polyvinylpyrrolidone, crosslinked cellulose,microcrystalline cellulose, silica, metallic oxides, calcium carbonate,talc, mica, stearic acid and metal salts thereof, for example, magnesiumstearate. Preferred materials are starches, modified starches andsilica. In one type of embodiment, the amount offiller/extender/antiblocking agent/detackifying agent in the watersoluble film can be in a range of about 1 wt. % to about 6 wt. %, orabout 1 wt. % to about 4 wt. %, or about 2 wt. % to about 4 wt. %, orabout 1 phr to about 6 phr, or about 1 phr to about 4 phr, or about 2phr to about 4 phr, for example.

An anti-block agent (e.g. SiO₂ and/or stearic acid)) can be present inthe film in an amount of at least 0.1 PHR, or at least 0.5 PHR, or atleast 1 PHR, or in a range of about 0.1 to 5.0 PHR, or about 0.1 toabout 3.0 PHR, or about 0.4 to 1.0 PHR, or about 0.5 to about 0.9 PHR,or about 0.5 to about 2 PHR, or about 0.5 to about 1.5 PHR, or 0.1 to1.2 PHR, or 0.1 to 4 PHR, for example 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8PHR, or 0.9 PHR.

If the anti-block agent is an SiO₂ particle, a suitable median particlesize for the anti-block agent includes a median size in a range of about3 or about 4 microns to about 11 microns, or about 4 to about 8 microns,or about 5 to about 6 microns, for example 5, 6, 7, 8, or 8 microns. Asuitable SiO₂ is an untreated synthetic amorphous silica designed foruse in aqueous systems.

Detergent Composition

The detergent composition may be in the form of free flowing powder, aliquid, a compacted solid, a gel or a mixture thereof.

The detergent composition may be in the form of a free flowing powder.Such a free flowing powder may have an average particle size diameter ofbetween 100 microns and 1500 microns, preferably between 100 microns and1000 microns, more preferably between 100 microns and 750 microns. Thoseskilled in the art will be aware of standard techniques to measureparticle size. The detergent composition may be a free flowing laundrydetergent composition.

The detergent composition may be a liquid. In relation to the liquiddetergent composition of the present invention, the term ‘liquid’encompasses forms such as dispersions, gels, pastes and the like. Theliquid composition may also include gases in suitably subdivided form.However, the liquid composition excludes forms which are non-liquidoverall, such as tablets or granules.

The detergent composition may be a liquid laundry detergent composition.The term ‘liquid laundry detergent composition’ refers to any laundrydetergent composition comprising a liquid capable of wetting andtreating fabric e.g., cleaning clothing in a domestic washing machine.

The laundry detergent composition is used during the main wash processbut may also be used as pre-treatment or soaking compositions.

Laundry detergent compositions include fabric detergents, fabricsofteners, 2-in-1 detergent and softening, pre-treatment compositionsand the like.

The laundry detergent composition may comprise an ingredient selectedfrom bleach, bleach catalyst, dye, hueing dye, brightener, cleaningpolymers including alkoxylated polyamines and polyethyleneimines, soilrelease polymer, surfactant, solvent, dye transfer inhibitors, chelant,builder, enzyme, perfume, encapsulated perfume, polycarboxylates,rheology modifiers, structurant, hydrotropes, pigments and dyes,opacifiers, preservatives, anti-oxidants, processing aids, conditioningpolymers including cationic polymers, antibacterial agents, pH trimmingagents such as hydroxides and alkanolamines, suds suppressors, andmixtures thereof.

Surfactants can be selected from anionic, cationic, zwitterionic,non-ionic, amphoteric or mixtures thereof. Preferably, the fabric carecomposition comprises anionic, non-ionic or mixtures thereof.

The anionic surfactant may be selected from linear alkyl benzenesulfonate, alkyl ethoxylate sulphate and combinations thereof.

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

The non-ionic surfactant may be selected from fatty alcohol alkoxylate,an oxo-synthesised fatty alcohol alkoxylate, Guerbet alcoholalkoxylates, alkyl phenol alcohol alkoxylates or a mixture thereof.Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.In one aspect, R¹ is an alkyl group, which may be primary or secondary,that comprises from about 9 to 15 carbon atoms, or from about 10 to 14carbon atoms. In one aspect, the alkoxylated fatty alcohols will also beethoxylated materials that contain on average from about 2 to 12ethylene oxide moieties per molecule, or from about 3 to 10 ethyleneoxide moieties per molecule.

The shading dyes employed in the present laundry detergent compositionsmay comprise polymeric or non-polymeric dyes, pigments, or mixturesthereof. Preferably the shading dye comprises a polymeric dye,comprising a chromophore constituent and a polymeric constituent. Thechromophore constituent is characterized in that it absorbs light in thewavelength range of blue, red, violet, purple, or combinations thereofupon exposure to light. In one aspect, the chromophore constituentexhibits an absorbance spectrum maximum from about 520 nanometers toabout 640 nanometers in water and/or methanol, and in another aspect,from about 560 nanometers to about 610 nanometers in water and/ormethanol.

Although any suitable chromophore may be used, the dye chromophore ispreferably selected from benzodifuranes, methine, triphenylmethanes,napthalimides, pyrazole, napthoquinone, anthraquinone, azo, oxazine,azine, xanthene, triphenodioxazine and phthalocyanine dye chromophores.Mono and di-azo dye chromophores are preferred.

The dye may be introduced into the detergent composition in the form ofthe unpurified mixture that is the direct result of an organic synthesisroute. In addition to the dye polymer therefore, there may also bepresent minor amounts of un-reacted starting materials, products of sidereactions and mixtures of the dye polymers comprising different chainlengths of the repeating units, as would be expected to result from anypolymerisation step.

The laundry detergent compositions can comprise one or more detergentenzymes which provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, β-glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, ormixtures thereof. A typical combination is a cocktail of conventionalapplicable enzymes like protease, lipase, cutinase and/or cellulase inconjunction with amylase.

The laundry detergent compositions of the present invention may compriseone or more bleaching agents. Suitable bleaching agents other thanbleaching catalysts include photobleaches, bleach activators, hydrogenperoxide, sources of hydrogen peroxide, pre-formed peracids and mixturesthereof.

The composition may comprise a brightener. Suitable brighteners arestilbenes, such as brightener 15. Other suitable brighteners arehydrophobic brighteners, and brightener 49. The brightener may be inmicronized particulate form, having a weight average particle size inthe range of from 3 to 30 micrometers, or from 3 micrometers to 20micrometers, or from 3 to 10 micrometers. The brightener can be alpha orbeta crystalline form.

The compositions herein may also optionally contain one or more copper,iron and/or manganese chelating agents. The chelant may comprise1-hydroxyethanediphosphonic acid (HEDP) and salts thereof;N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof;2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and anycombination thereof.

The compositions of the present invention may also include one or moredye transfer inhibiting agents. Suitable polymeric dye transferinhibiting agents include, but are not limited to, polyvinylpyrrolidonepolymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidoneand N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles ormixtures thereof.

The laundry detergent composition may comprise one or more polymers.Suitable polymers include carboxylate polymers, polyethylene glycolpolymers, polyester soil release polymers such as terephthalatepolymers, amine polymers, cellulosic polymers, dye transfer inhibitionpolymers, dye lock polymers such as a condensation oligomer produced bycondensation of imidazole and epichlorhydrin, optionally in ratio of1:4:1, hexamethylenediamine derivative polymers, and any combinationthereof.

Other suitable cellulosic polymers may have a degree of substitution(DS) of from 0.01 to 0.99 and a degree of blockiness (DB) such thateither DS+DB is of at least 1.00 or DB+2DS-DS' is at least 1.20. Thesubstituted cellulosic polymer can have a degree of substitution (DS) ofat least 0.55. The substituted cellulosic polymer can have a degree ofblockiness (DB) of at least 0.35. The substituted cellulosic polymer canhave a DS+DB, of from 1.05 to 2.00. A suitable substituted cellulosicpolymer is carboxymethylcellulose.

Another suitable cellulosic polymer is cationically modifiedhydroxyethyl cellulose.

Suitable perfumes include perfume microcapsules, polymer assistedperfume delivery systems including Schiff base perfume/polymercomplexes, starch-encapsulated perfume accords, perfume-loaded zeolites,blooming perfume accords, and any combination thereof. A suitableperfume microcapsule is melamine formaldehyde based, typicallycomprising perfume that is encapsulated by a shell comprising melamineformaldehyde. It may be highly suitable for such perfume microcapsulesto comprise cationic and/or cationic precursor material in the shell,such as polyvinyl formamide (PVF) and/or cationically modifiedhydroxyethyl cellulose (catHEC).

Suitable suds suppressors include silicone and/or fatty acid such asstearic acid.

The laundry detergent composition maybe coloured. The colour of theliquid laundry detergent composition may be the same or different to anyprinted area on the film of the article. Each compartment of the unitdose article may have a different colour. Preferably, the liquid laundrydetergent composition comprises a non-substantive dye having an averagedegree of alkoxylation of at least 16.

Other Compositions

The composition for use inside the unit dose article may be anon-detergent composition and/or a non-household care composition. Afabric or household care composition includes fabric treatments, hardsurfaces, air care, car care, dishwashing, fabric conditioning andsoftening, laundry detergency, laundry and rinse additive and/or care,hard surface cleaning and/or treatment, and other cleaning for consumeror institutional use. Non-household care compositions are for otheruses. For example, a non-household care composition can be selected fromagricultural compositions, aviation compositions, food and nutritivecompositions, industrial compositions, livestock compositions, marinecompositions, medical compositions, mercantile compositions, militaryand quasi-military compositions, office compositions, and recreationaland park compositions, pet compositions, water-treatment compositions,including cleaning and detergent compositions applicable to any such usewhile excluding fabric and household care compositions.

It is contemplated that one type of embodiment will include an articleas described herein with a sealed compartment containing a fabric careor household care composition, a film including a blend of a polyvinylalcohol homopolymer and an anionic polyvinyl alcohol copolymer, and boththe first water soluble film and the second water soluble film includeblends include 65 wt. % or greater of an anionic polyvinyl alcoholcopolymer.

It is contemplated that another type of embodiment will include anarticle as described herein with a sealed compartment containing afabric care or household care composition, a film including a blend ofat least two anionic polyvinyl alcohol copolymers, and both then firstwater soluble film and the second water soluble film include blends ofat least two anionic polyvinyl alcohol copolymers.

In one type of embodiment, the composition can include an agrochemical,e.g. one or more insecticides, fungicides, herbicides, pesticides,miticides, repellants, attractants, defoliaments, plant growthregulators, fertilizers, bactericides, micronutrients, and traceelements. Suitable agrochemicals and secondary agents are described inU.S. Pat. Nos. 6,204,223 and 4,681,228 and EP 0989803 A1. For example,suitable herbicides include paraquat salts (for example paraquatdichloride or paraquat bis(methylsulphate), diquat salts (for examplediquat dibromide or diquat alginate), and glyphosate or a salt or esterthereof (such as glyphosate isopropylammonium, glyphosate sesquisodiumor glyphosate trimesium, also known as sulfosate). Incompatible pairs ofcrop protection chemicals can be used in separate chambers, for exampleas described in U.S. Pat. No. 5,558,228. Incompatible pairs of cropprotection chemicals that can be used include, for example, bensulfuronmethyl and molinate; 2,4-D and thifensulfuron methyl; 2,4-D and methyl2-[[[[N-4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate;2,4-D and metsulfuron methyl; maneb or mancozeb and benomyl; glyphosateand metsulfuron methyl; tralomethrin and any organophosphate such asmonocrotophos or dimethoate; bromoxynil andN-[[4,6-dimethoxypyrimidine-2-yl)-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine-sulfonamide;bromoxynil and methyl2-[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-benzoate;bromoxynil and methyl2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate.In another, related, type of embodiment, the composition can include oneor more seeds, optionally together with soil, and further optionallytogether with one or more additional components selected from mulch,sand, peat moss, water jelly crystals, and fertilizers, e.g. includingtypes of embodiments described in U.S. Pat. No. 8,333,033.

In another type of embodiment, the composition is a water-treatmentagent. Such agents include aggressive oxidizing chemicals, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0110301 andU.S. Pat. No. 8,728,593. For example, sanitizing agents can includehypochlorite salts such as sodium hypochlorite, calcium hypochlorite,and lithium hypochlorite; chlorinated isocyanurates such asdichloroisocyanuric acid (also referred to as “dichlor” ordichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione)and trichloroisocyanuric acid (also referred to as “trichlor” or1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione). Salts and hydrates ofthe sanitizing compounds are also contemplated. For example,dichloroisocyanuric acid may be provided as sodium dichloroisocyanurate,sodium dichloroisocyanurate acid dihydrate, among others. Brominecontaining sanitizing agents may also be suitable for use in unit dosepackaging applications, such as 1,3-dibromo-5,5-dimethylhydantoin(DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyano aceticacid amide, 1-bromo-3-chloro-5,5-dimethylhydantoin; and2-bromo-2-nitro-1,3-propanediol, among others. The oxidizing agent canbe one described in U.S. Pat. No. 7,476,325, e.g. potassium hydrogenperoxymonosulfate. The composition can be a pH-adjusting chemical, e.g.as described in U.S. Patent Application Publication No. 2008/0185347,and can include, for example, an acidic component and an alkalinecomponent such that the composition is effervescent when contacted withwater, and adjusts the water pH. Suitable ingredients include sodiumbicarbonate, sodium bisulfate, potassium hydroxide, sulfamic acid,organic carboxylic acids, sulfonic acids, and potassium dihydrogenphosphate. A buffer blend can include boric acid, sodium carbonate,glycolic acid, and oxone monopersulfate, for example.

A water-treatment agent can be or can include a flocculant, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0124454. Theflocculant can include a polymer flocculant, e.g. polyacrylamide, apolyacrylamide copolymer such as an acrylamide copolymers ofdiallydimethylammonium chloride (DADMAC), dimethylaminoethylacrylate(DMAEA), dimethylaminoethylmethacrylate (DMAEM),3-methylamidepropyltrimethylammonium chloride (MAPTAC) or acrylic acid;a cationic polyacrylamide; an anionic polyacrylamide; a neutralpolyacrylamide; a polyamine; polyvinyl amine; polyethylene imine;polydimethyldiallylammonium chloride; poly oxyethylene; polyvinylalcohol; polyvinyl pyrrolidone; polyacrylic acid; polyphosphoric acid;polystyrene sulfonic acid; or any combination thereof. A flocculant canbe selected from chitosan acetate, chitosan lactate, chitosan adipate,chitosan glutamate, chitosan succinate, chitosan malate, chitosancitrate, chitosan fumarate, chitosan hydrochloride, and combinationsthereof. The water-treating composition can include a phosphate removingsubstance, e.g. one or more selected from a zirconium compound, a rareearth lanthanide salt, an aluminum compound, an iron compound, or anycombination thereof.

The composition can be a limescale removing composition, e.g. citric ormaleic acid or a sulphate salt thereof, or any mixture thereof, e.g. asdescribed in U.S. Patent Application No. 2006/0172910. Various othertypes of compositions are contemplated for use in the unit dose articlesdescribed herein, including particulates, for example down feathers,e.g. as described in U.S. RE29059 E; super absorbent polymers, e.g. asdescribed in U.S. Patent Application Publication Nos. 2004/0144682 and2006/0173430; pigments and tinters, e.g. as described in U.S. Pat. No.3,580,390 and U.S. Patent Application Publication No. 2011/0054111;brazing flux (e.g. alkali metal fluoroaluminates, alkali metalfluorosilicates and alkali metal fluorozincates), e.g. as described inU.S. Pat. No. 8,163,104; food items (e.g., coffee powder or dried soup)as described in U.S. Patent Application Publication No. 2007/0003719;and wound dressings, e.g. as described in U.S. Pat. No. 4,466,431.

At least one compartment of the unit dose article may comprise a solid.If present, the solid may be present at a concentration of at least 5%by weight of the unit dose article.

Method of Making a Unit Dose Article

Those skilled in the art will be aware of processes to make thedetergent or other composition of the present invention. Those skilledin the art will be aware of standard processes and equipment to make thedetergent or other compositions.

Those skilled in the art will be aware of standard techniques to makethe unit dose article according to any aspect of the present invention.Standard forming processes including but not limited to thermoformingand vacuum forming techniques may be used.

A preferred method of making the water-soluble unit dose articleaccording to the present invention comprises the steps of moulding thefirst water-soluble film in a mould to form an open cavity, filling thecavity with the detergent or orther composition, laying the second filmover the first film to close the cavity, and sealing the first andsecond films together preferably through solvent sealing, the solventpreferably comprising water, to produce the water-soluble unit dosearticle.

Test Protocols

Unit Dose Article Machine Wash Dissolution Test Method

This method is designed to assess the relative dissolution properties oflaundry water soluble unit dose articles under stressed washing machineconditions. For this method Electrolux Programmable Washing machinestype W565H, an adjusted EMPA221 load (EMPA221 source:Swissatest—SWISSatest testsmaterials, Movenstrasse 12 CH9015 St Gallen,Switzerland) and Digieye picture taking equipment (Digieye by VeriVide)were used.

The adjusted EMPA221 load was prepared by coloring the load into anorange color by using commercially available dying solutions for inwashing machines dying (Dylon goldfish orange washing machine dye (No55)). To color the load any standard household washing machine can beused, employing a standard cotton cycle at 40° C. 500 g of salt and 200g of the Dylon goldfish orange machine dye are added to the drum of thewashing machine. The drum was consequently moved to the left and theright until the salt and the dye were not visible anymore. 25 EMPA 221items (size of 50 cm×50 cm, overlocked on the edges to prevent fraying),were consequently evenly distributed over the drum without folding ofthe items. A standard cotton cycle at 40° C. was run at a water hardnessof 15 gpg. After completion of the cycle 50 g of Ariel Sensitive powderwas added into the dispenser and a normal cotton cycle at 40° C. was runat a water hardness of 15 gpg. After completion of this cycle 2additional normal cotton cycles at 40° C. without any detergent were runat a water hardness of 15 gpg, followed by line-drying the items.

To note: Brand new EMPA221 items must be desized before coloring them byadding 25 items into a front loading Miele washing machine and running 2short cotton cycles at 60° C. (approximate duration of 1 h 30) with 50 gof Ariel sensitive powder and a water hardness of 15 gpg, followed byrunning 2 more short cotton cycles at 60° C. (approximate duration of 1h 30) with no detergent and a water hardness of 15 gpg, followed bytumble drying.

The Electrolux W565 programmable washing machines were programmed with 2programs. The first program was designed to equally wet the load(pre-wet program). The second program (dissolution program) was utilizedto simulate 10 min of a Western Europe stressed cycle setting, followedby pumping out the water and starting a spin of 3 min at 1100 rpm.

Dissolution Pre-wet program program Wash Time 5 min 10 min Motorrotation 49 rpm 40 rpm Water intake 12 L 4 L Heating No heating Noheating Motor action time 28 s 28 s clockwise Motor resting time 12 s 12s Motor action time 28 s 28 s Counterclockwise Drain Draining time 20 s20 s Motor rotation 20 rpm 49 rpm Extraction Time NA 3 min Motorrotation NA 1100 rpm

A load consisting of 50 dyed EMPA221 fabrics (ca. 2.45 kg) was evenlyintroduced in the Electrolux W565 washing machine and the pre-wetprogram was started. After the pre-wet program, 6 water soluble unitdose articles were distributed evenly across the wet load, after whichthe dissolution program was initiated. At the end of the full program,the wet load was transferred to a grading room (equipped with D65lighting conditions) to be assessed for residues by expert graders. Eachfabric which had discoloration spots due to remnant detergent or excesspolymer resin, was selected out of the load for image analysis.

This image analysis was conducted by acquiring pictures of each side ofthe selected fabrics using the Digi-Eye camera (setting: “d90 DiffuseLight. Shutter time ¼. Aperture 8”). The fabrics should be put onto agray or black background to enhance the contrast. After this the imagewas assessed through image analysis software to calculate the total sizeof residue detected in the load (pixel count). This tool detectsresidues by identifying spots that are of a different color than thenormal ballast, using delta E thresholding (delta E of 6). For onemachine and load a residue score is then calculated by summing the totalarea of residues present in the load. The logarithmic value of the totalresidue area is calculated and the average of 4 external replicates,i.e. 4 different washing machine runs, was reported.

Unit Dose Article Strength and Seal Failure Test Method

This test method describes the practice for determining the unit dosearticle strength and seal failure using the Instron Universal MaterialsTesting instrument (Instron Industrial Products, 825 University Ave.,Norwood, Mass. 02062-2643) with a load cell of maximum 100 kN (kiloNewton). Via compression of a unit dose article, this method determinesthe overall strength (in Newtons) of the unit dose article by puttingpressure on the film and seal regions. Unit dose article strength (inNewtons) is defined as the maximum load a unit dose article can supportbefore it breaks. Unit dose articles opening at the seal area at apressure lower than 250N are reported as seal failures, and are nottaken into account when determining average unit dose article strength.

The unit dose article strength and seal failure is measured no soonerthan one hour after unit dose article production so that the film/unitdose articles had time to set after converting. The method was performedin a room environment between 30-40% relative humidity (RH) and 20-23°C. Stored unit dose articles were allowed to re-equilibrate to thetesting room environment for one hour prior to testing.

FIG. 1. shows a schematic illustration of the basic configuration of theunit dose article strength test and seal failure test. To measure unitdose article strength and seal failure, a unit dose article 510 wasenclosed in a plastic de-aerated bag 500 (150 mm by 124 mm with closure,60 micron thick—e.g. Raja grip RGP6B) to prevent contamination ofworking environment upon unit dose article rupture. After enclosure inthe bag, the unit dose article 510 is centered between two compressionplates 520, 530 of the instrument. The unit dose article 510 is placedin an upright position, so that the width seal dimension 540 (e.g.smallest dimension within a defined rectangular plane just encompassingthe seal area, 41 mm in actual unit dose articles tested) is between thecompression plates (x-direction) such that the stress is applied on thewidth seal. For the compression, the speed of decreasing the distancebetween the plates 520 and 530 is set at 60 mm/min. Ten replicates areconducted per test leg, and average unit dose article strength and sealfailure data are reported.

Tensile Strain Test and e-Modulus Test

A water-soluble film characterized by or to be tested for tensile strainaccording to the Tensile Strain (TS) Test and e-modulus (elongationmodulus or tensile stress) according to the Modulus (MOD) Test wasanalyzed as follows. The procedure includes the determination of tensilestrain and the determination of e-modulus according to ASTM D 882(“Standard Test Method for Tensile Properties of Thin PlasticSheeting”). An INSTRON tensile testing apparatus (Model 5544 TensileTester or equivalent—Instron Industrial Products, 825 University Ave.,Norwood, Mass. 02062-2643) was used for the collection of film data. Aminimum of three test specimens, each cut with reliable cutting tools(e.g. JDC precision sample cutter, Model 1-10, from Thwing AlbertInstrument Company, Philadelphia, Pa. U.S.A.) to ensure dimensionalstability and reproducibility, were tested in the machine direction (MD)(where applicable), i.e. water soluble film roll winding/unwindingdirection, for each measurement. Water soluble films werepre-conditioned to testing environmental conditions for a minimum of 48h. Tests were conducted in the standard laboratory atmosphere of 23±2.0°C. and 35±5% relative humidity. For tensile strain or modulusdetermination, 1″-wide (2.54 cm) samples of a single film sheet having athickness of 3.0±0.15 mil (or 76.2±3.8 μm) are prepared. For e-modulustesting virgin films were tested. For tensile strain testing test filmswere first pre-immersed in testing detergent according to the protocoldescribed below. The sample was then transferred to the INSTRON tensiletesting machine to proceed with testing. The tensile testing machine wasprepared according to manufacturer instructions, equipped with a 500 Nload cell, and calibrated. The correct grips and faces were fitted(INSTRON grips having model number 2702-032 faces, which are rubbercoated and 25 mm wide, or equivalent). The samples were mounted into thetensile testing machine, elongated at a rate of 1N/min, and analyzed todetermine the e-modulus (i.e., slope of the stress-strain curve in theelastic deformation region) and tensile strain at break (i.e., %elongation achieved at the film break, i.e. 100% reflects startinglength, 200% reflects a film that has been lengthened 2 times at filmbreak). The average of minimum three test specimens was calculated andreported.

Film Pre-Immersion Protocol

A film sample measuring 11 cm by 12 cm was prepared of both filmsintended to be used to form a sealed compartment enclosing a liquidhousehold detergent composition. A total of 750 ml of the householdliquid detergent composition intended to be enclosed within a sealedcompartment comprising the test films, was required for each test film.The bottom of a clean inert glass recipient was covered with a thinlayer of liquid and the film to be tested was spread on the liquid; airbubbles trapped under the film were gently pushed towards the sides. Theremaining liquid was then gently poured on top of the film, in such away that the film was fully immersed into the liquid. The film shouldremain free of wrinkles and no air bubbles should be in contact with thefilm. The film stayed in contact with the liquid and was stored underclosed vessel conditions for 6 days at 35° C. and 1 night at 21° C. Aseparate glass recipient was used for each test film. The film was thenremoved from the storage vessel, and the excess liquid was removed fromthe film. A piece of paper was put on the film which was laid on top ofa bench paper, and then the film was wiped dry thoroughly with drypaper. Films were consequently pre-conditioned to tensile strainenvironmental testing conditions as described above. When intendingenclosing solid household detergent compositions, virgin films were usedfor tensile strain testing.

Method for Measurement of Water Capacity

Water capacity was measured with a DVS (Dynamic Vapor Sorption)Instrument. The instrument used was a SPS-DVS (model SPSx-1μ-High loadwith permeability kit) from ProUmid. The DVS uses gravimetry fordetermination of moisture sorption/desorption and is fully automated.

The accuracy of the system is ±0.6% for the RH (relative humidity) overa range of 0-98% and ±0.3° C. at a temperature of 25° C. The temperaturecan range from +5 to +60° C. The microbalance in the instrument iscapable of resolving 0.1 μg in mass change. 2 replicates of each filmare measured and the average water capacity value is reported.

For the specific conditions of the test, a 6 pan carousel which allowsto test 5 films simultaneously (1 pan is used as a reference for themicrobalance and needs to remain empty) was used.

Each pan has an aluminum ring with screws, designed to fix the films. Apiece of film was placed onto a pan and after gentle stretching, thering was placed on top and the film was tightly fixed with the screwsand excess film removed. The film covering the pan surface had an 80 mmdiameter.

The temperature was fixed at 20° C. Relative humidity (RH) was set at35% for 6 hours, and then gradually raised onto 50% in 5 min. The RHremained at 50% for 12 hours. The total duration of the measurement was18 hours.

The cycle time (=time between measuring each pan) was set to 10 min andthe DVS records each weight result vs. time and calculates automaticallythe % Dm (relative mass variation versus starting weight of the film,i.e. 10% reflects a 10% film weight increase versus starting filmweight).

The water capacity (or % Dm gained over 50% RH cycle during the fixedtime of 12 hours at 20° C.) was calculated by difference of the value %Dm at 50% RH (last value measured at 50% RH) minus % Dm at 35% RH (lastvalue before going up to 50% RH).

Dissolution and Disintegration Test (MSTM 205)

A film can be characterized by or tested for Dissolution Time andDisintegration Time according to the MonoSol Test Method 205 (MSTM 205),a method known in the art and discussed in US20160024446.

The following embodiments are also contemplated:

1. A water soluble pouch comprising at least one sealed compartmentoptionally comprising at least one composition, the pouch comprising afirst water soluble film and a second water soluble film;

wherein the first water soluble film is sealed to the second watersoluble film to form the at least one sealed compartment;

wherein the first water soluble film has a first water capacity and afirst tensile strain at break;

wherein the second water soluble film has a second water capacity and asecond tensile strain at break;

wherein the first water capacity is less than the second water capacityand the difference between the first water capacity and the second watercapacity is from about 0.01 to about 1, or from about 0.03 to about 0.5or from about 0.05 to about 0.3

wherein the first tensile strain at break is greater than the secondtensile strain at break and the difference between the first tensilestrain at break and the second tensile strain at break is from about 10to about 1000 or from about 100 to about 750 or from about 200 to about500/

2. The water soluble pouch of embodiment 1, wherein the first watersoluble film has a first elongation modulus, the second water solublefilm has a second elongation modulus, the first elongation modulus isgreater than the second elongation modulus, and the difference betweenthe first elongation modulus and the second elongation modulus is fromabout 0.5 mPa to about 10 mPa, or from about 1 mPa to about 8 mPa, orfrom about 2 mPa to about 7 mPa.

3. The water soluble pouch according to any one of the precedingembodiments, wherein the first water capacity is from about 4 to about6.

4. The water soluble pouch according to any one of the precedingembodiments, wherein the second water capacity is from about 4 to about6

5. The water soluble pouch according to any one of the precedingembodiments, wherein the first tensile strain at break is from about 500to about 1200, or about 700 to about 1200, or about 900 to about 1200.

6. The water soluble pouch according to any one of the precedingembodiments, wherein the second tensile strain at break is from about500 to about 1200, or about 500 to about 1000, or about 500 to about900.

7. The water soluble pouch of embodiment 2, wherein the first elongationmodulus is from about 8 to about 20, or from about 10 to about 20.

8. The water soluble pouch of embodiment 2, wherein the secondelongation modulus is from about 8 to about 20, or from about 8 to about15.

9. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film is thermoformed priorto incorporation into the pouch.

10. The water soluble pouch according to any one of the precedingembodiments, wherein the second water soluble film is not thermoformedprior to incorporation into the pouch.

11. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film and the second watersoluble film each has a thickness of about 76 microns and dissolutiontime prior to incorporation into the pouch of about 300 seconds or lessin water at a temperature of 20° C. in accordance with MonoSol TestMethod MSTM-205.

12. The water soluble pouch according to any one of the precedingembodiments, wherein the pouch has a pouch strain of at least about 200N as measured by the first water soluble film sealed, conditioned, andtested according to the Pouch Strain Test.

13. The water soluble pouch according to any one of the precedingembodiments, wherein the second water soluble film has a tackiness valueprior to incorporation into the pouch of at least about 1500 inaccordance with the Tackiness PA Test

14. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film comprises a firstwater soluble resin and the second water soluble film comprises a secondwater soluble resin.

15. The water soluble pouch of embodiment 14, wherein the first watersoluble resin comprises a polyvinyl alcohol or copolymer thereof and thesecond water soluble resin comprises a polyvinyl alcohol or a copolymerthereof.

16. The water soluble pouch of embodiment 14, wherein the first watersoluble resin comprises a blend of a polyvinyl alcohol homopolymer and apolyvinyl alcohol copolymer comprising an anionic monomer unit.

17. The water soluble pouch of embodiment 16, wherein the blendcomprises from about 30 to about 100 weight percent of the polyvinylalcohol copolymer comprising an anionic monomer unit and from about 0 toabout 70 weight percent of the polyvinyl alcohol homopolymer, based onthe total weight of polyvinyl alcohol in the film.

18. The water soluble pouch of embodiment 17, wherein the blendcomprises from about 30 to about 70 weight percent, or from about 30 toabout 65 weight percent, or from about 30 to about 50 weight percent ofthe polyvinyl alcohol copolymer comprising an anionic monomer unit,based on the total weight of polyvinyl alcohol in the film.

19. The water soluble pouch of embodiment 14, wherein the second watersoluble resin comprises a blend of a polyvinyl alcohol homopolymer and apolyvinyl alcohol copolymer comprising an anionic monomer unit.

20. The water soluble pouch of embodiment 19, wherein the blendcomprises from about 30 to about 100 weight percent of the polyvinylalcohol copolymer comprising an anionic monomer unit and from about 0 toabout 70 weight percent of the polyvinyl alcohol homopolymer, based onthe total weight of polyvinyl alcohol in the film.

21. The water soluble pouch of embodiment 20, wherein the blendcomprises from about 30 to about 70 weight percent, or from about 30 toabout 65 weight percent, or from about 30 to about 50 weight percent ofthe polyvinyl alcohol copolymer comprising an anionic monomer unit,based on the total weight of polyvinyl alcohol in the film.

22. The water soluble pouch of any one of embodiments 16 to 21, whereinthe anionic monomer unit is selected from the group consisting of vinylacetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkylmaleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaricacid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate,dimethyl fumarate, fumaric anhydride, itaconic acid, monomethylitaconate, dimethyl itaconate, itaconic anhydride, citraconic acid,monoalkyl citraconate, dialkyl citraconate, citraconic anhydride,mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconicanhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate,glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methyl propane sulfonic acid,2-acrylamide-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkalimetal salts thereof, esters thereof, and combinations thereof.

23. The water soluble pouch of embodiment 22, wherein the anionicmonomer unit is selected from the group consisting of maleic acid,monoalkyl maleate, dialkyl maleate, maleic anhydride, alkali metal saltsthereof, esters thereof, and combinations thereof.

24. The water soluble pouch of embodiment 23, wherein the anionicmonomer unit is selected from the group consisting of maleic acid,monomethyl maleate, dimethyl maleate, maleic anyhydride, alkali metalsalts thereof, esters thereof, and combinations thereof.

25. The water soluble pouch of any one of embodiments 16 to 24, whereinthe polyvinyl alcohol copolymer comprises from about 2 mol % to about 8mol % of the anionic monomer unit, or from about 1 mol % to about 4 mol% of the anionic monomer unit.

26. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble resin comprises polyvinylalcohol having a degree of hydrolysis in a range of about 87 to about93.

27. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble resin comprises a blend ofa polyvinyl alcohol homopolymer and a polyvinyl alcohol copolymercomprising an anionic monomer unit, wherein the blend has an arithmeticweight average degree of hydrolysis in the range of about 87 to about93.

28. The water soluble pouch according to any one of the precedingembodiments, wherein the pouch has a pouch strain of less than 2000 N asmeasured by the first water soluble film sealed, conditioned, and testedaccording to the Burst Strength Test.

29. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film further comprises aplasticizer.

30. The water soluble pouch according to any one of the precedingembodiments, wherein the second water soluble film further comprises aplasticizer.

31. The water soluble pouch of embodiment 31 or embodiment 32, whereinthe plasticizer is selected from the group consisting of glycerine,trimethylol propane, sorbitol, and combinations thereof.

32. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film further comprises asurfactant.

33. The water soluble pouch according to any one of the precedingembodiments, wherein the second water soluble film further comprises asurfactant.

34. The water soluble pouch of embodiment 34 or embodiment 35, whereinthe surfactant is selected from the group consisting ofpolyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols, alkanolamides,polyoxyethylenated amines, quaternary ammonium salts, quaternizedpolyoxyethylenated amines, amine oxides, N-alkylbetaines, sulfobetaines,and mixtures thereof.

35. The water soluble pouch according to any one of the precedingembodiments, wherein the first water soluble film further comprises anaversive agent.

36. The water soluble pouch according to any one of the precedingembodiments, wherein the second water soluble film further comprises anaversive agent.

37. The water soluble pouch according to any one of the precedingembodiments, wherein the thickness of the first water soluble film doesnot vary from the thickness of the second water soluble film by morethan 10%.

38. The water soluble pouch according to embodiment 14, wherein thefirst water soluble resin has a 4% solution viscosity at 25° C. in arange of about 12 cP to about 40 cP, or about 12 cP to about 30 cP, orabout 14 cP to about 25 cP.

39. The water soluble pouch according to embodiment 14, wherein thesecond water soluble resin has a 4% solution viscosity at 25° C. in arange of about 4 cP to about 35 cP, or about 10 cP to about 20 cP, orabout 10 cP to about 15 cP, or about 12 cP to about 14 cP.

40. The water soluble pouch according to embodiment 14, wherein the 4%solution viscosity at 25° C. of the first water soluble resin is greaterthan the 4% solution viscosity at 25° C. of the second water solubleresin and the difference between the 4% solution viscosity at 25° C. ofthe first water soluble resin and the 4% solution viscosity at 25° C. ofthe second water soluble resin is about 2 cP about 20 cP, or about 3 cPto about 15 cP, or about 4 cP to about 12 cP.

41. The water soluble pouch according to any one of the precedingembodiments, wherein the composition in the sealed compartment is anon-household care composition.

EXAMPLES

The following unit dose articles are prepared and tested for unit dosearticle strength, seal failure, and pouch dissolution per the protocolsdescribed herein. Comparative unit dose article(s) outside the scope ofthe invention are prepared out of a single film type while example unitdose articles according to the invention are prepared out of twodifferent films, differing in molecular weight of the homopolymer.

Multi-compartment water soluble unit dose articles with a 41 mm×43 mmfootprint, cavity depth of 20.1 mm and cavity volume of 25 ml, are madethrough thermo/vacuum forming. For dual film example unit dose articlefilm A is deformed under vacuum while film B is used as a closing film.A standard detergent composition, as commercially available in the UK inJanuary 2016 in the bottom compartment of Fairy non-Bio 3-in-1 watersoluble unit dose article product was enclosed inside these singlecompartment unit dose articles.

Table 1 below details film compositions used to prepare unit dosearticles.

TABLE 1 Polymer 2 (PVOH Resin Polymer 1 (anionic-PVOH copolymer)homopolymer) content Blend Anionic Anionic 4% 4% in film ratio sourcesubstition dH viscosity dH viscosity Case 1 Film A 65% 30/70 Monomethyl4% 89% 16 cps 88% 18 cps maleate (carboxylated) Film B 65% 50/50Monomethyl 4% 89% 16 cps 88% 18 cps maleate (carboxylated) Film C 65%70/30 Monomethyl 4% 89% 16 cps 88% 18 cps maleate (carboxylated)

Unit dose articles, e.g., pouches, made from films having increasedanionic content exhibit increased stickiness. By combining films thatare chemically different from each other, with respect to the anioniccontent of the films, a water-soluble unit dose article exhibitingoptimal dissolution and reduced stickiness may be obtained.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A water-soluble unit dose article comprising atleast one sealed compartment optionally comprising at least onecomposition contained in the article, the water-soluble unit dosearticle comprising a first water soluble film comprising a PVOH polymercomprising a first anionic content; and a second water soluble filmcomprising a PVOH polymer comprising a second anionic content; whereinthe first anionic content is in a range of about 0.5 mol % to about 10mol % of total PVOH polymer in the first water soluble film and thesecond anionic content is in a range of about 0 mol % to about 5 mol %of total PVOH polymer in the second water soluble film, and thedifference between the first anionic content and second anionic contentis about 0.05 mol % to about 4 mol %, wherein the anionic content ofeach film is the molar percentage of anionic monomer units present inthe total PVOH polymer of the film, and wherein the first water-solublefilm is chemically different from the second water soluble film withrespect to the anionic content of the PVOH polymers of the films;wherein the first film is sealed to the second film to form the at leastone sealed compartment; wherein the first water soluble film comprises afirst water soluble PVOH resin and the second water soluble filmcomprises a second water soluble PVOH resin; wherein the first watersoluble resin comprises a first blend of at least one polyvinyl alcoholcopolymer comprising an anionic monomer unit(s) and at least onepolyvinyl alcohol homopolymer, the second water soluble resin comprisesa second blend of at least one polyvinyl alcohol copolymer comprising ananionic monomer unit(s) and at least one polyvinyl alcohol homopolymer,and the first blend is chemically different from the second blend; andwherein the first blend comprises a monomethyl maleate modified PVOHresin and a PVOH homopolymer resin and the second blend comprises amonomethyl maleate modified PVOH resin and a PVOH homopolymer resin;provided that when the composition is a fabric care or household carecomposition and a film comprises a blend of a polyvinyl alcoholhomopolymer resin and an anionic polyvinyl alcohol copolymer resin, thenboth the first water soluble film and the second water soluble filmcomprise blends that include 65 wt. % or greater of an anionic polyvinylalcohol copolymer resin, based on the total weight of polyvinyl alcoholresins in the blend; and provided that when the composition is a fabriccare or household care composition and a film comprises a blend of atleast two anionic polyvinyl alcohol copolymer resins, then both thenfirst water soluble film and the second water soluble film compriseblends of at least two anionic polyvinyl alcohol copolymer resins. 2.The water-soluble unit dose article of claim 1, wherein the firstanionic content is greater than the second anionic content.
 3. Thewater-soluble unit dose article according to claim 1, wherein the firstwater soluble resin comprises a first blend of two or more polyvinylalcohol copolymers comprising anionic monomer unit(s), the second watersoluble resin comprises a second blend of two or more polyvinyl alcoholcopolymers comprising anionic monomer unit(s), and the first blend ischemically different from the second blend.
 4. The water-soluble unitdose article of claim 1, wherein the first water soluble resin comprisesfrom 65% by weight or greater of the first water soluble resin of thepolyvinyl alcohol copolymer comprising an anionic monomer unit and thesecond water soluble resin comprises from 65% by weight or greater ofthe second water soluble resin of the polyvinyl alcohol copolymercomprising an anionic monomer unit.
 5. The water-soluble unit dosearticle of claim 1, wherein the first water soluble resin comprises fromabout 1% to about 70% by weight of the first water soluble resin of thepolyvinyl alcohol copolymer comprising an anionic monomer unit and fromabout 30% to about 99% by weight of the first water soluble resin of thepolyvinyl alcohol homopolymer.
 6. The water-soluble unit dose article ofclaim 5, wherein the first water soluble resin comprises from about 10wt % to about 70 wt % by weight of the first water soluble resin of thepolyvinyl alcohol copolymer comprising an anionic monomer unit.
 7. Thewater-soluble unit dose article of claim 1, wherein the second watersoluble resin comprises from about 1 wt % to about 70 wt % by weight ofthe second water soluble resin of the polyvinyl alcohol copolymercomprising an anionic monomer unit and from about 30 wt % to about 99 wt% by weight of the second water soluble resin of the polyvinyl alcoholhomopolymer.
 8. The water-soluble unit dose article of claim 7, whereinthe second water soluble resin comprises from about 10 wt % to about 70wt % by weight of the second water soluble resin of the polyvinylalcohol copolymer comprising an anionic monomer unit.
 9. Thewater-soluble unit dose article of claim 1, wherein the first watersoluble resin comprises from about 10 wt % to about 32 wt % by weight ofthe first water soluble resin of the polyvinyl alcohol copolymercomprising an anionic monomer unit and the second water soluble resincomprises from about 33 wt % to about 50 wt % by weight of the secondwater soluble resin of the polyvinyl alcohol copolymer comprising ananionic monomer unit.
 10. The water-soluble unit dose article of claim1, wherein the first water soluble resin comprises at least onepolyvinyl alcohol copolymer(s) comprising from about 2 mol % to about 8mol % of the anionic monomer unit with respect to total polyvinylalcohol copolymer present.
 11. The water-soluble unit dose article ofclaim 1, wherein the second water soluble resin comprises at least onepolyvinyl alcohol copolymer(s) comprising from about 2 mol % to about 8mol % of the anionic monomer unit with respect to total polyvinylalcohol copolymer present.
 12. The water-soluble unit dose article ofclaim 1, wherein the first water soluble resin comprises at least onepolyvinyl alcohol copolymer(s) comprising from about 1 mol % to about 3mol % of the anionic monomer unit with respect to total polyvinylalcohol copolymer present and the second water soluble resin comprisesat least one polyvinyl alcohol copolymer(s) comprising from about 4 mol% to about 8 mol % of the anionic monomer unit with respect to totalpolyvinyl alcohol copolymer present.
 13. The water-soluble unit dosearticle according to claim 1, wherein the first water soluble film is athermoformed film.
 14. The water-soluble unit dose article according toclaim 13, wherein the second water soluble film is not a thermoformedfilm.
 15. The water-soluble unit dose article according to claim 1,wherein the anionic content of the a first water soluble film or the asecond water soluble film further comprises an anionic monomer unitderived from a monomer selected from the group consisting of vinylacetic acid, alkyl acrylates, maleic acid, monoalkyl maleate other thanmonomethyl maleate, dialkyl maleate, dimethyl maleate, maleic anhydride,fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate,dimethyl fumarate, fumaric anhydride, itaconic acid, monomethylitaconate, dimethyl itaconate, itaconic anhydride, citraconic acid,monoalkyl citraconate, dialkyl citraconate, citraconic anhydride,mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconicanhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate,glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methyl propane sulfonic acid,2-acrylamide-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts thereof, esters thereof, and combinations thereof.16. The water-soluble unit dose article of claim 1, wherein the PVOHresin of the first water soluble film comprises a first anionic content,the PVOH resin of the second water soluble film comprises a secondanionic content, and the first anionic content is greater than thesecond anionic content.
 17. The water-soluble unit dose articleaccording to claim 1, wherein the water-soluble unit dose article is apouch and has a pouch strength of less than about 2000 N in accordancewith the Pouch Strength Test.
 18. The water-soluble unit dose articleaccording to claim 1, wherein the first water-soluble film and thesecond water-soluble film each independently comprises from about 30 wt% to about 90 wt % by weight of the film of water-soluble resin.
 19. Thewater-soluble unit dose article according to claim 1, wherein the firstwater-soluble film and the second water-soluble film each independentlyhas a thickness prior to incorporation into the water-soluble unit dosearticle of about 40 microns to about 100 microns.
 20. The water-solubleunit dose article according to claim 1, wherein the first water-solublefilm and the second water-soluble film each independently has adissolution time prior to incorporation into the water-soluble unit dosearticle of about 300 seconds or less in water at a temperature of 20° C.for a film having a thickness of about 76 micron in accordance withMonoSol Test Method MSTM-205.
 21. The water-soluble unit dose articleaccording to claim 1, wherein the water-soluble unit dose article has anaverage Log(residue area) of less than about 6.2 per the unit dosearticle machine wash dissolution test method.
 22. The water-soluble unitdose article according to claim 1, wherein the thickness of the firstwater soluble film does not vary from the thickness of the second watersoluble film by more than 10%.
 23. The water-soluble unit dose articleaccording to claim 1, wherein the thickness of the first water-solublefilm is the same as the thickness of the second water-soluble film. 24.The water-soluble unit dose article according to claim 1, wherein thewater-soluble unit dose article is a pouch and has a pouch strength ofat least about 350N in accordance with the Pouch Strength Test.
 25. Thewater-soluble unit dose article according to claim 1, wherein thewater-soluble unit dose article has 0 seal failures in accordance withthe Seal Failure Test.
 26. The water soluble unit dose article accordingto claim 1, wherein the water-soluble unit dose article is a pouch andhas a pouch strength of at least about 350N in accordance with the PouchStrength Test, the water-soluble unit dose article has 0 seal failuresin accordance with the Seal Failure Test, and the water-soluble unitdose article has an average Log(residue area) of less than about 6.2 perthe unit dose article machine wash dissolution test method.
 27. Thewater-soluble unit dose article according to claim 1, wherein the firstwater soluble film further comprises a plasticizer.
 28. Thewater-soluble unit dose article according to claim 1, wherein the secondwater soluble film further comprises a plasticizer.
 29. Thewater-soluble unit dose article of claim 27, wherein the plasticizer isselected from the group consisting of glycerine, trimethylol propane,sorbitol, and combinations thereof.
 30. The water-soluble unit dosearticle according to claim 1, wherein the first water soluble filmfurther comprises a surfactant.
 31. The water-soluble unit dose articleaccording to claim 1, wherein the second water soluble film furthercomprises a surfactant.
 32. The water-soluble unit dose article of claim30, wherein the surfactant is selected from the group consisting ofpolyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols, alkanolamides,polyoxyethylenated amines, quaternary ammonium salts, quaternizedpolyoxyethylenated amines, amine oxides, N-alkylbetaines, sulfobetaines,and mixtures thereof.
 33. The water-soluble unit dose article accordingto claim 1, wherein the first water soluble film further comprises anaversive agent.
 34. The water-soluble unit dose article according toclaim 1, wherein the second water soluble film further comprises anaversive agent.
 35. The water-soluble unit dose article according toclaim 1, wherein the water-soluble unit dose article comprises at leasttwo sealed compartments, or at least three sealed compartments.
 36. Thewater-soluble unit dose article according to claim 35, wherein the unitdose article comprises a top film, a middle film, and a bottom film, thetop and bottom films comprising the first water-soluble film and themiddle film comprising the second water-soluble film.
 37. Thewater-soluble unit dose article according to claim 1, wherein the firstwater soluble resin comprises a polyvinyl alcohol copolymer having adegree of hydrolysis in a range of about 80% to about 99%.
 38. Thewater-soluble unit dose article according to claim 1, wherein the secondwater soluble resin comprises a polyvinyl alcohol copolymer having adegree of hydrolysis in a range of about 80% to about 99%.
 39. Thewater-soluble unit dose article according to claim 1, wherein the firstwater soluble resin comprises a polyvinyl alcohol homopolymer having adegree of hydrolysis in a range of about 80% to about 99%.
 40. Thewater-soluble unit dose article according to claim 1, wherein the secondwater soluble resin comprises a polyvinyl alcohol homopolymer having adegree of hydrolysis in a range of about 80% to about 99%.
 41. Thewater-soluble unit dose article according to claim 1, wherein thearticle contains a non-household care composition.
 42. The water-solubleunit dose article according to claim 41, wherein the non-household carecomposition is selected from agricultural compositions, aviationcompositions, food and nutritive compositions, industrial compositions,livestock compositions, marine compositions, medical compositions,mercantile compositions, military and quasi-military compositions,office compositions, and recreational and park compositions, petcompositions, water-treatment compositions.
 43. The water-soluble unitdose article according to claim 42, wherein the non-household carecomposition comprises an agricultural composition.
 44. The water-solubleunit dose article according to claim 42, wherein the non-household carecomposition comprises an water-treatment composition.
 45. A method ofmaking a water soluble unit dose article comprising a compositioncontained in the article; comprising the steps of: contacting a firstwater-soluble film and a second water-soluble film along a seal area;sealing the first water soluble film and the second water soluble filmtogether, thereby enclosing the composition in the water soluble unitdose article; wherein the first water-soluble film comprises a PVOHpolymer comprising a first anionic content and the second water solublefilm comprises a PVOH polymer comprising a second anionic content,wherein the first water-soluble film and the second water-soluble filmare chemically different to one another with respect to the anioniccontent of the PVOH polymers of the films; wherein the first anioniccontent is in a range of about 0.5 mol % to about 10 mol % of total PVOHpolymer in the first water soluble film and the second anionic contentis in a range of about 0 mol % to about 5 mol % of total PVOH polymer inthe second water soluble film, and the difference between the firstanionic content and second anionic content is about 0.05 mol % to about4 mol %; wherein the first water soluble film comprises a first watersoluble PVOH resin and the second water soluble film comprises a secondwater soluble PVOH resin; wherein the first water soluble resincomprises a first blend of at least one polyvinyl alcohol copolymercomprising an anionic monomer unit(s) and at least one polyvinyl alcoholhomopolymer, the second water soluble resin comprises a second blend ofat least one polyvinyl alcohol copolymer comprising an anionic monomerunit(s) and at least one polyvinyl alcohol homopolymer, and the firstblend is chemically different from the second blend; and wherein thefirst blend comprises a monomethyl maleate modified PVOH resin and aPVOH homopolymer resin and the second blend comprises a monomethylmaleate modified PVOH resin and a PVOH homopolymer resin; provided thatwhen the composition is a fabric care or household care composition anda film comprises a blend of a polyvinyl alcohol homopolymer resin and ananionic polyvinyl alcohol copolymer resin, then both then first watersoluble film and the second water soluble film comprise blends thatinclude 65 wt. % or greater of an anionic polyvinyl alcohol copolymerresin, based on the total weight of polyvinyl alcohol resins in theblend; and provided that when the composition is a fabric care orhousehold care composition and a film comprises a blend of at least twoanionic polyvinyl alcohol copolymer resins, then both then first watersoluble film and the second water soluble film comprise blends of atleast two anionic polyvinyl alcohol copolymer resins.
 46. Method ofusing a first water-soluble film and a second water-soluble film tomanufacture a water-soluble unit dose article with improved sealstrength and optionally comprising a composition contained in thearticle, wherein the first water-soluble film comprises a PVOH polymercomprising a first anionic content and the second water soluble filmcomprises a PVOH polymer comprising a second anionic content, whereinthe first water-soluble film and the second water-soluble film arechemically different to one another with respect to the anionic contentof the PVOH polymers of the films; wherein the first anionic content isin a range of about 0.5 mol % to about 10 mol % of total PVOH polymer inthe first water soluble film and the second anionic content is in arange of about 0 mol % to about 5 mol % of total PVOH polymer in thesecond water soluble film, and the difference between the first anioniccontent and second anionic content is about 0.05 mol % to about 4 mol %;wherein the first water soluble film comprises a first water solublePVOH resin and the second water soluble film comprises a second watersoluble PVOH resin; wherein the first water soluble resin comprises afirst blend of at least one polyvinyl alcohol copolymer comprising ananionic monomer unit(s) and at least one polyvinyl alcohol homopolymer,the second water soluble resin comprises a second blend of at least onepolyvinyl alcohol copolymer comprising an anionic monomer unit(s) and atleast one polyvinyl alcohol homopolymer, and the first blend ischemically different from the second blend; and wherein the first blendcomprises a monomethyl maleate modified PVOH resin and a PVOHhomopolymer resin and the second blend comprises a monomethyl maleatemodified PVOH resin and a PVOH homopolymer resin; comprising sealing thefirst film and the second film together along a seal area, in order toimprove the seal strength in the seal area; provided that when thecomposition is a fabric care or household care composition and a filmcomprises a blend of a polyvinyl alcohol homopolymer resin and ananionic polyvinyl alcohol copolymer resin, then both then first watersoluble film and the second water soluble film comprise blends thatinclude 65 wt. % or greater of an anionic polyvinyl alcohol copolymerresin, based on the total weight of polyvinyl alcohol resins in theblend; and provided that when the composition is a fabric care orhousehold care composition and a film comprises a blend of at least twoanionic polyvinyl alcohol copolymer resins, then both then first watersoluble film and the second water soluble film comprise blends of atleast two anionic polyvinyl alcohol copolymer resins.
 47. A process fordosing a unit dose article according to claim 1 comprising the steps of:obtaining a water-soluble unit dose article according to claim 1; andcontacting the article with water to dissolve at least one of the films.48. The water-soluble unit dose article of claim 1 comprising at leastone sealed compartment comprising at least one composition contained inthe article, wherein the first anionic content ranges from about 1 mol %to about 4 mol % of total PVOH polymer in the first water soluble filmand the second anionic content ranges from about 0.1 mol % to about 3mol % of total PVOH polymer in the second water soluble film, and thedifference between the first anionic content and second anionic contentis about 0.05 mol %.
 49. The water-soluble unit dose article of claim48, wherein the first blend of PVOH polymer resins comprises from about10 wt % to about 70 wt % by weight of monomethyl maleate modified PVOHresin.
 50. The water-soluble unit dose article of claim 48, wherein thesecond blend of PVOH polymer resins comprises from about 10 wt % toabout 70 wt % by weight of monomethyl maleate modified PVOH resin. 51.The water-soluble unit dose article of claim 48, wherein the first blendof PVOH polymer resins comprises from about 10 wt % to about 32 wt % byweight of monomethyl maleate modified PVOH resin and the second blend ofPVOH polymer resins comprises from about 33 wt % to about 50 wt % byweight of monomethyl maleate modified PVOH resin.
 52. The water-solubleunit dose article according to claim 48, wherein the first water solublefilm is a thermoformed film.
 53. The water-soluble unit dose articleaccording to claim 48, wherein the second water soluble film is not athermoformed film.
 54. The water-soluble unit dose article according toclaim 48, wherein the anionic content of the a first water soluble filmor the a second water soluble film further comprises an anionic monomerunit derived from a monomer selected from the group consisting of vinylacetic acid, alkyl acrylates, maleic acid, monoalkyl maleate other thanmonomethyl maleate, dialkyl maleate, dimethyl maleate, maleic anhydride,fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate,dimethyl fumarate, fumaric anhydride, itaconic acid, monomethylitaconate, dimethyl itaconate, itaconic anhydride, citraconic acid,monoalkyl citraconate, dialkyl citraconate, citraconic anhydride,mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconicanhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate,glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methyl propane sulfonic acid,2-acrylamide-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts thereof, esters thereof, and combinations thereof.55. The water-soluble unit dose article of claim 54, wherein the furtheranionic monomer unit is derived from a monomer selected from the groupconsisting of maleic acid, monoalkyl maleate other than monomethylmaleate, dialkyl maleate, maleic anhydride, alkali metal salts thereof,esters thereof, and combinations thereof.
 56. The water-soluble unitdose article according to claim 48, wherein the monomethyl maleatemodified PVOH resin has a degree of hydrolysis in a range of about 80%to about 99%.
 57. The water-soluble unit dose article according to claim48, wherein the PVOH homopolymer resin has a degree of hydrolysis in arange of about 80% to about 99%.